EP2234132B1 - Élément de conversion photoélectrique comportant des particules de diamant ou de nitrure de bore - Google Patents

Élément de conversion photoélectrique comportant des particules de diamant ou de nitrure de bore Download PDF

Info

Publication number
EP2234132B1
EP2234132B1 EP10168992.5A EP10168992A EP2234132B1 EP 2234132 B1 EP2234132 B1 EP 2234132B1 EP 10168992 A EP10168992 A EP 10168992A EP 2234132 B1 EP2234132 B1 EP 2234132B1
Authority
EP
European Patent Office
Prior art keywords
electrolyte
gel
ionic liquid
photoelectric conversion
particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP10168992.5A
Other languages
German (de)
English (en)
Other versions
EP2234132A2 (fr
EP2234132A3 (fr
Inventor
Hiroki Usui
Nobuo Tanabe
Hiroshi Matsui
Tetsuya Ezure
Shozo Yanagida
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujikura Ltd
Original Assignee
Fujikura Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujikura Ltd filed Critical Fujikura Ltd
Publication of EP2234132A2 publication Critical patent/EP2234132A2/fr
Publication of EP2234132A3 publication Critical patent/EP2234132A3/fr
Application granted granted Critical
Publication of EP2234132B1 publication Critical patent/EP2234132B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
    • H01G9/2009—Solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
    • H01G9/2013—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte the electrolyte comprising ionic liquids, e.g. alkyl imidazolium iodide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
    • H01M14/005—Photoelectrochemical storage cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2036—Light-sensitive devices comprising an oxide semiconductor electrode comprising mixed oxides, e.g. ZnO covered TiO2 particles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
    • H10K30/821—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes comprising carbon nanotubes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
    • Y10S977/742—Carbon nanotubes, CNTs

Definitions

  • the present invention relates to a photoelectric conversion element comprising an ionic liquid and insulating particles, wherein the insulating particles are selected from diamond and boron nitride.
  • Dye-sensitized photovoltaic cells were developed by Graetzel et al. in Switzerland. They have advantages, such as low cost, and are attracting attention as new types of photoelectric conversion cells (see, for example, Japanese Patent No. 2664194 : Japanese Unexamined Patent Application, First Publication No. 2001-160427 , and Michael Graetzel, Nature, United Kingdom, 1991, vol. 737, p. 353 ).
  • Dye-sensitized photovoltaic cells generally include a transparent conductive electrode substrate, a working electrode that has a porous film made of oxide semiconductor fine particles (nanoparticles), such as titanium dioxide, and is sensitized with a photo-sensitizing dye on the electrode substrate, a counter electrode provided opposing the working electrode, and an electrolyte containing an oxidation-reduction pair filled between the working electrode and the counter electrode.
  • a dye-sensitized photovoltaic cell functions as a photoelectric conversion element that converts light energy into electricity when the oxide semiconductor fine particles are sensitized by the photo-sensitizing dye that absorbs incident light, such as sunlight, thereby generating an electromotive force between the working electrode and the counter electrode.
  • an electrolyte solution is typically used in which an oxidation-reduction pair, such as I - /I 3 - , is dissolved in an organic solvent, such as acetonitrile.
  • organic solvent such as acetonitrile.
  • electrolytes include one using a nonvolatile ionic liquid, one in which the liquid electrolyte is made into a gel using an appropriate gelling agent to be quasi-solidified, and one using a solid semiconductor, such as a p-type semiconductor.
  • An ionic liquid is also called a room temperature molten salt, exists as a stable liquid in a broad temperature region, including in the vicinity of room temperature, and is a salt made from a cation and an anion. Since ionic liquids have very low vapor pressure and do not substantially vaporize at room temperature, they are not liable to volatilization or cause ignition, unlike typical organic solvents. Thus, they are proposed as a solution to a problem of decrease in cell characteristics caused by volatilization (see N. Papageorgiou et al., Journal of the Electrochemical Society (J. Electrochem. Soc.), United Kingdom, 1996, vol. 143 (10), p. 3099 ), for example.
  • electrolyte solution liquid
  • electrolyte solution liquid
  • electrolyte solution liquid
  • electrolyte solution fluid leakage
  • an appropriate gelling agent see Japanese Unexamined Patent Application, First Publication No. 2002-184478 , for example.
  • ionic liquids suffer from a shortcoming in that the electrical resistance thereof is higher than that of an electrolyte solution obtained through dissolution into an organic solvent, such as acetonitrile.
  • gelling agents conventionally used for gel electrolytes include, for example, polyvinylidene fluoride, polyvinylidene fluoride - hexafluoropropylene copolymer, polyethylene oxide derivatives, polyacrylonitrile derivatives, amino acid derivatives.
  • these gelling agents have a shortcoming in that the conversion efficiency of a photoelectric conversion element is significantly reduced compared to a case without adding such gelling agents since they are electrical insulators having very high electrical resistances.
  • a problem to be solved by the present invention is to provide a photoelectric conversion element that exhibits the conversion efficiency comparable to that of one using liquid electrolytes (electrolyte solutions), and a dye-sensitized photovoltaic cell using the same.
  • the present invention provides a photoelectric conversion element comprising an electrolyte composition comprising an ionic liquid (A) and insulating particles (C) as main components, wherein the ionic liquid includes a compound containing a quaternized nitrogen atom as a cation, and wherein the insulating particles are at least one member chosen from the group consisting of diamond and boron nitride, and wherein the electrolyte composition is made into a gel by the action of the cation and the insulating particles.
  • A ionic liquid
  • C insulating particles
  • a compounding amount of the conductive particles (C) be no less than 0.05% by weight and no more than 70% by weight with respect to the total amount of the electrolyte composition.
  • the present invention provides a photoelectric conversion element, comprising: a working electrode, the working electrode comprising an electrode substrate and an oxide semiconductor porous film formed on the electrode substrate and sensitized with a dye; a counter electrode disposed opposing the working electrode; and an electrolyte layer made of the electrolyte composition defined in claim 1 provided between the working electrode and the counter electrode.
  • the present invention provides a dye-sensitized photovoltaic cell, comprising: a working electrode, the working electrode comprising an electrode substrate and an oxide semiconductor porous film formed on the electrode substrate and sensitized with a dye; a counter electrode disposed opposing the working electrode; and an electrolyte layer made of the electrolyte composition defined in claim 1 provided between the working electrode and the counter electrode.
  • a gel electrolyte having a high conductivity can be obtained by making an ionic liquid into a gel.
  • an electrolyte composition as an electrolyte of a photoelectric conversion element, it becomes possible to stably achieve high output characteristics and photoelectric conversion characteristics.
  • the electrolyte composition is in a state of a gel, it has reduced flowability, thereby achieving excellent safety and durability and ease of handling.
  • FIG. 1 is a schematic diagram illustrating an example of a photoelectric conversion element according to the present invention.
  • ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide was used, and an electrolyte solution containing iodine/iodide ions as an oxidation-reduction pair was prepared by dissolving appropriate amounts of iodine and lithium iodide, and an appropriate amount of 4- tert -butylpyridine into this ionic liquid.
  • Electrolyte compositions of Examples A-1 to A-10 were obtained by blending carbon nanotubes, or carbon fibers, or carbon black as conductive particles in the above electrolyte solution at a ratio of 1% by weight with respect to the total amount of the electrolyte composition and then centrifuging the mixture.
  • the compounding amount of the conductive particles with respect to the ionic liquid was about 1.25% by weight.
  • a transparent electrode substrate As a transparent electrode substrate, a 100 mm x 100 mm glass substrate having an FTO film formed thereon was provided, and a slurry dispersion solution of titanium oxide having an average particle diameter of 20 nm was applied on the FTO film (conductive layer) side surface of this transparent electrode substrate 2. After being dried, an oxide semiconductor porous film having a thickness of 7 ⁇ m was obtained by performing heating treatment at 450°C for one hour. The transparent electrode substrate was then immersed overnight in an ethanol solution of ruthenium bipyridine complex (an N3 dye) so as to be sensitized with the dye to form a working electrode. Furthermore, as a counter electrode, an FTO glass electrode substrate was prepared having an electrode layer made of platinum formed thereon by sputtering.
  • the electrolyte composition that was made into a gel was dropped to the oxide semiconductor porous film of the working electrode in a small amount, and then the counter electrode and the electrolyte layer were adhered together by overlaying them while pressing the counter electrode hard.
  • dye-sensitized photovoltaic cells which were test cells of Examples A1-1 to A1-5, A2, and A3 were fabricated.
  • Electrodes similar to those used in the above-described test cells of Examples A1-1 to A1-5, A2, and A3 were used.
  • an electrolyte solution to form an electrolyte an ionic liquid [1-cthyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide] containing iodine/iodide ions as an oxidation-reduction pair was prepared and used.
  • This electrolyte solution was similar to those used to prepare the electrolyte solutions for the electrolyte compositions of the test cells of Examples A1-1 to A1-5, A2, and A3, except that conductive particles were not added.
  • a dye-sensitized photovoltaic cell which was the test cell of Comparative Example A1 was fabricated by placing the working electrode and the counter electrode so that they opposed each other and forming an electrolyte layer by injecting the electrolyte solution therebetween.
  • Electrodes similar to those used in the above-described test cells of Examples A1-1 to A1-5, A2, and A3 were used.
  • an electrolyte solution to form an electrolyte an acetonitrile solution containing quaternary imidazolium-iodide, lithium iodide, iodine, and 4- tert -butylpyridine was prepared and used.
  • a dye-sensitized photovoltaic cell which was the test cell of Comparative Example A2 was fabricated by placing the working electrode and the counter electrode so that they opposed each other and forming an electrolyte layer by injecting the electrolyte solution therebetween.
  • Example A1-1 Carbon nanotubes 100% / 0% gel 4.4
  • Example A1-2 Carbon nanotubes 80% / 20% gel 4.4
  • Example A1-3 Carbon nanotubes 50% / 50% gel 4.5
  • Example A1-4 Carbon nanotubes 20% / 80% gel 4.3
  • Example A1-5 Carbon nanotubes 0% / 100% gel 4.7
  • Example A2 Carbon fibers - gel 4.4
  • Example A3 Carbon black - gel 4.3 Comparative Example A1 none - liquid 4.1 Comparative Example A2 none (acetonitrile solution) - liquid 5.5
  • an electrolyte composition as an electrolyte of a photoelectric conversion element, it becomes possible to stably achieve high output characteristics and photoelectric conversion characteristics. Furthermore, since the electrolyte composition is in a state of a gel, it has reduced flowability, thereby achieving excellent safety and durability and ease of handling.
  • EMIm-TFSI 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
  • EMIm-TFSI 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
  • an electrolyte solution containing iodine/iodide ions as an oxidation-reduction pair was prepared by dissolving appropriate amounts of 1-ethyl-3-methylimidazolium iodide (EMIm-I), iodine, lithium iodide, and an appropriate amount of 4- tert -butylpyridine into this ionic liquid.
  • EMIm-I 1-ethyl-3-methylimidazolium iodide
  • 4- tert -butylpyridine 4- tert -butylpyridine
  • Electrolyte compositions of Examples B-1 to B-10 were obtained as follows. Nanoparticles of titanium dioxide (in Table 2, shown labeled as "TiO 2 ”) having an average particle diameter of between 2 nm and 1000 nm as oxide semiconductor particles (B) were blended into the above electrolyte solution (one including EMIm-TFSI as an ionic liquid) so that the total amount with respect to the electrolyte solution was 10% by weight (Example B-1).
  • nanoparticles of titanium dioxide and carbon nanotubes in Table 2, shown labeled as "CNT" as conductive particles (C) were blended such that the total compounding amount of the particles was 1% by weight with respect to the total amount of the electrolyte solution in the compounding ratio shown in Table 2 (the values are represented when the total compounding amount of the particles is regarded as 100%) (Examples B-2 to B-10).
  • the mixtures were then centrifuged to obtain electrolyte compositions of Examples B-1 to B-10 in which the ionic liquid formed a gel.
  • SWCNT single-wall carbon nanotubes
  • MWCNT multi-wall carbon nanotubes
  • Table 2 values under each of the labels of "TiO 2 ,” “SWCNT,” and “MWCNT” represent compounding ratios in % by weight of each particle in the total compounding amount before centrifuging the particles (1% by weight with respect to the total amount of the electrolyte solution).
  • the column labeled "Ratio of Particles after Centrifugation" in Table 2 lists the ratio of particles insoluble in the ionic liquid after centrifugation of the particles (in this example, the sum of TiO 2 nanoparticles and CNTs) when the total electrolyte composition is regarded as 100%.
  • Electrolyte compositions of Examples B-11 to B-14 were obtained as follows. Titanium oxide nanotubes as oxide semiconductor particles (B) were blended into the above electrolyte solution (one including EMIm-TFSI as an ionic liquid) so that the total amount with respect to the electrolyte solution was 10% by weight (Example B-11). Alternatively, titanium oxide nanotubes and titanium oxide nanoparticles were blended such that the total compounding amount of the particles was 10% by weight with respect to the total amount of the electrolyte solution in the compounding ratio shown in Table 3 (the values are represented when the total compounding amount of the particles is regarded as 100%) (Examples B-12 to B-14). The mixtures were then centrifuged to obtain electrolyte compositions of Examples B-11 to B-14 in which the ionic liquid formed a gel.
  • the column labeled "Ratio of Particles after Centrifugation" in Table 3 lists the ratio of particles insoluble in the ionic liquid after centrifugation of the particles (in this example, the sum of nanotubes and nanoparticles made of TiO 2 ) when the total electrolyte composition is regarded as 100%.
  • Electrolyte compositions of Examples B-15 to B-17 were obtained as follows. Titanium oxide nanotubes (CNTs) as oxide semiconductor particles (B) and carbon nanotubes as conductive particles (C) were blended into the above electrolyte solution (one including EMIm-TFSI as an ionic liquid) such that the total compounding amount of the particles was 1 % by weight with respect to the total amount of the electrolyte solution in the compounding ratio shown in Table 4 (the values are represented when the total compounding amount of the particles is regarded as 100%) (Examples B-15 to B-17). The mixtures were then centrifuged to obtain electrolyte compositions of Examples B-15 to B-17 in which the ionic liquid formed a gel. In Examples B-15 to B-17, MWCNTs were used as carbon nanotubes.
  • the column labeled "Ratio of Particles after Centrifugation" in Table 4 lists the ratio of particles insoluble in the ionic liquid after centrifugation of the particles (in this example, the sum of the titanium oxide nanoparticles and carbon nanotubes) when the total electrolyte composition is regarded as 100%.
  • Electrolyte compositions of Examples B-18 to B-25 were obtained as follows. Various nanoparticles made from materials listed in the column of "Oxide Semiconductor Particles" of Table 5 as oxide semiconductor particles (B) were blended into the above electrolyte solution (one including EMIm-TFSI as an ionic liquid) such that the amount of the particles was 10% by weight with respect to the total amount of the electrolyte solution (the values are represented when the total compounding amount of the particles is regarded as 100%). The mixtures were then centrifuged to obtain electrolyte compositions of Examples B-18 to B-25 in which the ionic liquid formed a gel.
  • oxide semiconductor particles one including EMIm-TFSI as an ionic liquid
  • 1-hexyl-3-methylimidazolium iodide (this may be abbreviated as "HMIm-I”) or 1-ethyl-3-methylimidazolium dicyanoimide (this may be abbreviated as "EMIm-DCA”) was used, and an electrolyte solution containing iodine/iodide ions as an oxidation-reduction pair was prepared by dissolving appropriate amounts of EMIm-I, iodine, and lithium iodide, and an appropriate amount of 4- tert -butylpyridine into this ionic liquid.
  • HMIm-I 1-hexyl-3-methylimidazolium iodide
  • EMIm-DCA 1-ethyl-3-methylimidazolium dicyanoimide
  • Electrolyte compositions of Examples B-26 and B-27 were obtained as follows. Nanoparticles of titanium dioxide (in Table 2, shown labeled as "TiO 2 ") having an average particle diameter of between 2 nm and 1000 nm as oxide semiconductor particles (B) were blended so that the amount with respect to the total amount of the electrolyte solution was 10% by weight. The mixtures were then centrifuged to obtain electrolyte compositions of Examples B-26 and B-27 in which the ionic liquid formed a gel.
  • TiO 2 titanium dioxide having an average particle diameter of between 2 nm and 1000 nm as oxide semiconductor particles
  • a transparent electrode substrate As a transparent electrode substrate, a 100 mm x 100 mm glass substrate having an FTO film formed thereon was provided, and a slurry dispersion solution of titanium oxide having an average particle diameter of 20 nm was applied on the FTO film (conductive layer) side surface of this transparent electrode substrate 2. After being dried, an oxide semiconductor porous film having a thickness of 7 ⁇ m was obtained by performing heating treatment at 450°C for one hour. The transparent electrode substrate was then immersed overnight in an ethanol solution of ruthenium bipyridine complex (an N3 dye) so as to be sensitized with the dye to form a working electrode. Furthermore, as a counter electrode, an FTO glass electrode substrate was prepared having an electrode layer made of platinum formed thereon by sputtering.
  • the electrolyte composition that was made into a gel was dropped to the oxide semiconductor porous film of the working electrode in a small amount, and then the counter electrode and the electrolyte layer were adhered together by overlaying them while pressing the counter electrode hard.
  • dye-sensitized photovoltaic cells which were test cells of Examples B-1 to B-27 were fabricated.
  • Electrodes similar to those used in the above-described test cells of Examples B-1 to B-27 were used.
  • an electrolyte solution to form an electrolyte an ionic liquid [1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIm-TFSI)] containing iodine/iodide ions as an oxidation-reduction pair was prepared and used.
  • This electrolyte solution was similar to those used to prepare the electrolyte solutions for the electrolyte compositions of the test cells of Examples B-1 to B-27, except that oxide semiconductor particles (B), or oxide semiconductor particles (B) and conductive particles (C) were not added.
  • a dye-sensitized photovoltaic cell which was the test cell of Comparative Example B-1 was fabricated by placing the working electrode and the counter electrode so that they opposed each other and forming an electrolyte layer by injecting the electrolyte solution therebetween.
  • Electrodes similar to those used in the above-described test cells of Examples B-1 to B-27 were used.
  • an electrolyte solution to form an electrolyte an acetonitrile solution containing quaternary imidazolium-iodide, lithium iodide, iodine, and 4- tert -butylpyridine was prepared and used.
  • a dye-sensitized photovoltaic cell which was the test cell of Comparative Example B-2 was fabricated by placing the working electrode and the counter electrode so that they opposed each other and forming an electrolyte layer by injecting the electrolyte solution therebetween.
  • Electrodes similar to those used in the above-described test cells of Examples B-1 to B-27 were used.
  • an electrolyte solution to form an electrolyte an ionic liquid containing iodine/iodide ions as an oxidation-reduction pair was prepared and used.
  • HMIm-I was used in Comparative Example B-3
  • EMIm-DCA was used in Comparative Example B-4.
  • These electrolyte solutions were similar to those used to prepare the electrolyte solutions for the electrolyte compositions of the test cells of Examples B-1 to B-27 shown in Table 6, except that oxide semiconductor particles (B), or oxide semiconductor particles (B) and conductive particles (C) were not added.
  • Dye-sensitized photovoltaic cells which were the test cell of Comparative Examples B-3 and B-4 were fabricated by placing the working electrode and the counter electrode so that they opposed each other and forming an electrolyte layer by injecting the electrolyte solution therebetween.
  • Example B-1 100 - - 15.3% gel 5.0
  • Example B-2 80 20 - 11.2% gel 4.7
  • Example B-3 50 50 - 5.2 % gel 4.5
  • Example B-4 20 80 - 4.3 % gel 4.3
  • Example B-5 80 - 20 5.2 % gel 4.7
  • Example B-6 50 - 50 3.2% gel 4.8
  • Example B-7 20 - 80 2.3% gel 4.3
  • Example B-8 80 10 10 7.6% gel 4.9
  • Example B-9 60 20 20 4.1% gel 4.9
  • Example B-10 40 40 1.5% gel 4.7
  • Comparative Example B-1 ionic liquid only liquid 4.1
  • Comparative Example B-2 acetonitrile solution of redox pair liquid 5.5
  • Table 3 Titanium Oxide Nanotubes Titanium Oxide Nanoparticles Ratio of Particles after Centrifugation State Conversion Efficiency (%)
  • Example B-11 100% 0% 10.2% gel 5.1
  • Example B-12 80% 20% 11.2% gel 5.2
  • Example B-13 50% 50% 15.2% gel 5.0
  • the cases where the ionic liquid solutions were a gel (pseudo-solid) by means of addition of these particles and the cases where the ionic liquid solutions were a liquid without addition of the particles were compared.
  • a better electrolyte composition could be prepared when the oxide semiconductor particles (B), or the oxide semiconductor particles (B) and the conductive particle (C) were added to the ionic liquid solution (electrolyte solution), compared to cases when they were not added.
  • EMIm-TFSI 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
  • HMIm-I 1-hexyl-3-methylimidazolium iodide
  • EMIm-DCA 1-ethyl-3-methylimidazolium dicyanoimide
  • electrolyte compositions of the present invention obtained by blending the above-described liquid electrolyte and oxide semiconductor particles (B) listed in Table 7 were used.
  • Gel electrolytes of Comparative Examples B-5 and B-6 were obtained by making the liquid electrolyte into a gel (quasi-solid) using the gelling agents listed in Table 8.
  • PVdF-HFP represents a fluororesin-based gelling agent (polyvinylidene fluoride-hexafluoropropylene copolymer).
  • a low molecular weight gelling agent a commercially available low molecular weight gelling agent was used.
  • the gel electrolyte is one having a composition where oxide semiconductor particles (B) or gelling agents were added to a liquid electrolyte.
  • a "liquid electrolyte corresponding to a gel electrolyte” refers to a liquid electrolyte having a composition in which the oxide semiconductor particles (B) or gelling agents are omitted from that gel electrolyte.
  • a diffusion coefficient measured using a liquid electrolyte is termed as a diffusion coefficient in a liquid system
  • a diffusion coefficient measured using a gel electrolyte is termed as a diffusion coefficient in a gel system
  • a rate of change in the diffusion coefficients is termed as (the diffusion coefficient in the gel system - the diffusion coefficient in the liquid system / the diffusion coefficient in the liquid system).
  • An equilibrium potential measured using a liquid electrolyte is termed as an equilibrium potential in a liquid system
  • an equilibrium potential measured using a gel electrolyte is termed as a equilibrium potential in a gel system
  • a shift width of the equilibrium potentials is termed as (the equilibrium potential in the gel system - the equilibrium potential in the liquid system).
  • dye-sensitized photovoltaic cells were fabricated using the gel electrolytes and liquid electrolytes listed in Table 7 and Table 8.
  • the measurement conditions for the photoelectric conversion characteristics were photoirradiation conditions with an air mass (AM) of 1.5 and an irradiance of 100 mW/cm 2 .
  • an electrolyte having better characteristics than an ionic liquid (A) itself can be obtained by adding oxide semiconductor particles (B), or oxide semiconductor particles (B) and conductive particle (C) into an ionic liquid (A).
  • a photoelectric conversion element comprising an electrolyte composition
  • said electrolyte composition comprises an ionic liquid (A) and insulating particles (C), and wherein the insulating particles are at least one member chosen from the group consisting of diamond and boron nitride, the ionic liquid includes a compound containing a quaternized nitrogen atom as a cation, and wherein the electrolyte composition is made into a gel by the action of the cation and the insulating particles.
  • an electrolyte is regarded as a gel if all of 10 cc of the electrolyte that is placed into a columnar glass tube having an inner diameter of 15 mm and a depth of 10 cm does not fall to the bottom after 15 minutes at room temperature (23°C) when the glass tube is turned upside down.
  • the electrolyte composition contains an ionic liquid (A) as a first essential component.
  • the ionic liquid (A) is a room temperature molten salt that is liquid at room temperature and contains a compound containing a quaternized nitrogen atom as a cation.
  • the cation of the room temperature molten salt may be quaternary imidazolium derivatives, quaternary pyridinium derivatives, quaternary pyrrolidinium derivatives, quaternary ammonium derivatives, and the like.
  • 1,3-dialkyl imidazoliums such as, 1-ethyl-3-methylimidazolium, 1-ethyl-3-propyl imidazolium, 1-ethyl-3-hexyl imidazolium, 1-hexyl-3-methylimidazolium, are exemplified, for example.
  • N-alkyl pyridiniums such as N-butyl pyridinium, are exemplified, for example.
  • N,N-dialkyl pyrrolidiniums such as N-methyl-N-propyl pyrrolidinium and N-methyl-N-butyl pyrrolidinium, are exemplified.
  • the anion of the room temperature molten salt may be BF 4 - , PF 6 - , F(HF) n - , bis(trifluoromethylsulfonyl)imide [N(CF 3 SO 2 ) 2 - ], iodide ions, bromide ions, dicyanamide, and the like.
  • ionic liquid (A) may include salts made of a quaternary imidazolium cation, and iodide ion or bis(trifluoromethylsulfonyl)imide ion, dicyanamide ion, and the like.
  • the electrolyte composition contains insulating particles (C) as a second essential component.
  • the insulating particles (C) are one member or a mixture of two or more members selected from the group consisting of diamond and boron nitride (BN).
  • the size of insulating particles (C) is chosen so that they exhibit a miscibility with the electrolyte solution, which contains an ionic liquid as a main component, and can make the electrolyte solution into a gel.
  • the conductive particles do not cause a decrease in the conductivity in the electrolyte composition, and exhibit chemical stability to other co-existing components contained in the electrolyte composition.
  • the conductive particles do not degraded by an oxidation reaction even when the electrolyte composition contains an oxidation-reduction pair, such as iodine/iodide ion or bromine/bromide ion.
  • the insulating particles (C) are preferably nanoparticles.
  • Nanoparticles are particles having a particle size in the order of nanometer (i.e., less than 1000 nm). When nanoparticles have a tubular shape, it is suffice that their diameter (miner diameter) be in the order of nanometer and the length (major diameter) be several micrometers or greater.
  • the compounding amount of the insulating particles (C) be no less than 0.05% by weight and no more than 70% by weight with respect to the total amount of the electrolyte composition. More preferably, it is preferable that it be no less than 0.05% by weight and no more than 50% by weight.
  • Setting the compounding amount of the insulating particles (C) within the above range can enable the electrolyte solution containing the ionic liquid (A) to form a gel, and the electrolyte solution is prevented from being exposed and leaking (fluid leakage) during the manufacturing processes or upon breakage of the cell.
  • the compounding amount of the insulating particles (C) is less than 0.05% by weight with respect to the total amount of the electrolyte composition, the ionic liquid does not form a gel and fluid leakage or the like may occur upon breakage. In contrast, if the compounding amount of the insulating particles (C) exceeds 70% by weight with respect to the total amount of the electrolyte composition, the particles (C) may absorb all of the ionic liquid and the solution may not function as an electrolyte.
  • Oxidation-reduction pairs may be added to the electrolyte composition according to the third embodiment of the present invention, although they are not an essential component. It is preferable to add an oxidation-reduction pair when the electrolyte composition is used in a dye-sensitized photovoltaic cell or the like.
  • a halogen-based redox pair made of halide ions, such as iodide ions (I - ), bromide ions (Br - ), or chloride ions (Cl - ), or polyhalide ions, such as I 3 - , I 5 - , I 7 - , Br 3 - , Cl 2 I - , ClI 2 - , Br 2 I - , BrI 2 - , is preferably used, although these are not limiting.
  • halide ions such as iodide ions (I - ), bromide ions (Br - ), or chloride ions (Cl - )
  • polyhalide ions such as I 3 - , I 5 - , I 7 - , Br 3 - , Cl 2 I - , ClI 2 - , Br 2 I - , BrI 2 - , is preferably used, although these are not limiting.
  • pairs such as iodine/iodide ions, bromine/bromide ions, and the like may be added and obtained as the oxidation-reduction pair.
  • a lithium salt, quaternary imidazolium salt, tetrabutylammonium salt, and the like may be used alone or in combination.
  • additives or solvents such as tert -butylpyridine, may be added to the electrolyte composition according to the third embodiment of the present invention if required, as long as properties or characteristics of the electrolyte composition are not affected.
  • the methods for preparing the electrolyte composition from the components described above are not particularly limited, and a method may be employed, for example, in which an electrolyte solution is obtained by adding additives (components soluble in the ionic liquid), such as an oxidation-reduction pair, to an ionic liquid (A) and then blending the above-described insulating particles (C) (i.e., components insoluble in the ionic liquid) into the electrolyte solution to form a gel.
  • additives components soluble in the ionic liquid
  • insulating particles i.e., components insoluble in the ionic liquid
  • any of appropriate well-known agitators, mixers, or centrifugal separators may be used.
  • This electrolyte composition is used in photoelectric conversion elements, such as dye-sensitized photovoltaic cells, for example.
  • Cations (imidazolium ions, for example) are absorbed to surfaces of the nanoparticles in the gel electrolyte and counter anions (I - or I 3 - ) are arranged so that they encircle the cations.
  • concentration of redox pairs is increased locally on the surfaces of the nanoparticles.
  • cases have been reported where charges transfer by means of a conjugation of physical diffusion and electron exchange reaction in an electrolyte, and the latter, i.e., a more rapid charge transfer process, is accelerated in a composition where the redox concentration is high.
  • the electrolyte is made into a gel, the electrolyte solution is prevented from being exposed and leaking (fluid leakage) during the manufacturing processes or upon breakage of the cell, providing good productivity and easy handling.
  • FIG. 1 is a cross-sectional view showing an example of a schematic structure of a dye-sensitized photovoltaic cell, as an embodiment of the photoelectric conversion element of the present invention.
  • This dye-sensitized photovoltaic cell 1 includes a transparent electrode substrate 2, a working electrode 6 having an oxide semiconductive porous film 5 made of oxide semiconductive fine particles formed on the transparent electrode substrate 2 and sensitized with a photo-sensitizing dye, and a counter electrode 8 provided opposing the working electrode 6.
  • the above-described electrolyte composition is filled between the working electrode 6 and the counter electrode 8 to form an electrolyte layer 7.
  • the transparent electrode substrate 2 is made by forming the conductive layer 3 made of a conductive material on a transparent base material 4, such as a glass plate or a plastic sheet.
  • the transparent base material 4 is preferably made of a material having excellent optical transparent properties when taking its function into consideration.
  • transparent plastic sheets made of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyether sulfone (PES), or the like; a polished plate of a ceramic, such as titanium oxide, alumina, or the like, may be used.
  • transparent oxide semiconductors such as tin-doped indium oxide (ITO), tin oxide (SnO 2 ), fluorine-doped tin oxide (FTO), or the like, be used either alone or in a mixture of two or more thereof when taking the light transmittance of the transparent electrode substrate 2 into consideration.
  • ITO indium oxide
  • SnO 2 tin oxide
  • FTO fluorine-doped tin oxide
  • these materials are not limiting, and any suitable material having light transmittance and conductivity appropriate for an intended purpose may be used.
  • a metal wiring layer made of gold, silver, platinum, aluminum, nickel, titanium, or the like may be used provided that an area ratio of the metal wiring layer is within the range that does not significantly reduce the light transmittance of the transparent electrode substrate 2.
  • the metal wiring layer may be provided as a grid-like, stripe-like, or comb-like pattern so that light transmits through the transparent electrode substrate 2 as evenly as possible.
  • the method used to form the conductive layer 3 is not particularly limited, and examples thereof include thin film formation methods, such as a sputtering method, or a CVD method, or a spray decomposition method (SPD), or an evaporation method, when the conductive layer 3 is formed from ITO.
  • the conductive layer 3 is formed to a thickness of between about 0.05 ⁇ m and 2.0 ⁇ m considering the optical transparent properties and the conductivity.
  • the oxide semiconductor porous film 5 is a porous thin layer with a thickness between about 0.5 and 50 ⁇ m containing as a main component oxide semiconductor fine particles that are made of titanium dioxide (TiO 2 ), tin oxide (SnO 2 ), tungsten oxide (WO 3 ), zinc oxide (ZnO), and niobium oxide (Nb 2 O 5 ), used either alone or in a combination of two or more materials, and have an average particle diameter between 1 nm to 1000 nm.
  • TiO 2 titanium dioxide
  • SnO 2 tin oxide
  • WO 3 tungsten oxide
  • ZnO zinc oxide
  • Nb 2 O 5 niobium oxide
  • the oxide semiconductor porous film 5 can be formed, for example, by employing methods such as a method in which a dispersion solution obtained by dispersing commercially available oxide semiconductor fine particles in a desired dispersion medium is coated, or a colloidal solution that can be prepared using a sol-gel method is coated, after desired additives have been added thereto if these are required, using a known coating method such as a screen printing method, an inkjet printing method, a roll coating method, a doctor blade method, a spin coating method, a spray coating method, or the like.
  • a known coating method such as a screen printing method, an inkjet printing method, a roll coating method, a doctor blade method, a spin coating method, a spray coating method, or the like.
  • Electrophoretic deposition method in which the electrode substrate 2 is immersed in a colloidal solution and oxide semiconductor fine particles are made to adhere to the electrode substrate 2 by electrophoresis; a method in which a foaming agent is mixed in a colloidal solution or dispersion solution which is then coated and baked so as to form a porous material; and a method in which polymer microbeads are mixed together and coated on, and these polymer microbeads are then removed by thermal treatment or chemical treatment, so as to define spaces and thereby form a porous material.
  • the sensitizing dye that is provided in the oxide semiconductor porous film 5 is not particularly limited, and it is possible to use ruthenium complexes or iron complexes containing a ligand having bipyridine structures, terpyridine structures, and the like; metal complexes such as porphyrin and phthalocyanine; as well as organic dyes such as eosin, rhodamine, melocyanine, and coumarin.
  • the dye can be selected according to the application and the material used for the oxide semiconductor porous film.
  • the counter electrode 8 may be one obtained by forming a thin film made of a conductive oxide semiconductor, such as ITO, FTO, or the like, on a substrate made of a non-conductive material, such as a glass, or one obtained by forming an electrode by evaporating or applying a conductive material, such as gold, platinum, a carbon-based material, and the like, on a substrate. Furthermore, the counter electrode 8 may be one obtained by forming a layer of platinum, carbon, or the like, on a thin film of a conductive oxide semiconductor, such as ITO, FTO, or the like.
  • a conductive oxide semiconductor such as ITO, FTO, or the like
  • a method for forming the counter electrode 8 includes, forming a platinum layer by applying chloroplatinate and then performing a heat treatment, for example.
  • a method may be used in which the electrode is formed on a substrate by an evaporation technique or sputtering technique.
  • the method for forming the electrolyte layer 7 made of the above-described electrolyte composition on the working electrode 6 is not particularly limited, and a method may he employed in which the electrolyte composition is dropped on the working electrode 6 in a small amount.
  • the electrolyte layer may be formed by coating the electrolyte on the working electrode 6 or the counter electrode 8. By this, it is possible to make the electrolyte composition infiltrate into the spaces in the oxide semiconductor porous film 5 when the electrolyte composition is cast onto the working electrode 6.
  • the electrolyte composition is in a state of a gel in the photoelectric conversion element of the present invention that can be obtained with the above-described procedures, it has reduced volatility and flowability. Thus, degradation or loss of the electrolyte due to vaporization of the solvent or the like does not occur, and it becomes possible to stably achieve high output characteristics and photoelectric conversion characteristics. Furthermore, leakage of the electrolyte from the gap of a container or scattering thereof upon breakage of a photoelectric conversion element are prevented, providing better safety, durability, and the like compared to the cases where a liquid electrolyte solution is used.
  • a dye-sensitized photovoltaic cell according to the present invention includes the above-described photoelectric conversion element.
  • degradation or loss of the electrolyte due to vaporization of the solvent or the like does not occur, and it becomes possible to stably achieve high output characteristics and photoelectric conversion characteristics.
  • leakage of the electrolyte from the gap of a container or scattering thereof upon breakage of a photoelectric conversion element are prevented, providing better safety, durability, and the like compared to the cases where a liquid electrolyte solution is used.
  • EMIm-TFSI 1-ethyl-3-methylimidazolium bis(tritluoromethylsultonyl)imide
  • EMIm-TFSI 1-ethyl-3-methylimidazolium bis(tritluoromethylsultonyl)imide
  • Electrolyte compositions of Examples C- and C-2 were obtained as follows. Insulating particles (C) listed in Table 9 were blended as the insulating particles (C) into the electrolyte solution including EMIm-TFSI as an ionic liquid such that the amount of the particles was 10% by weight with respect to the total amount of the electrolyte solution (Examples D-1 and D-2). The mixtures were then centrifuged to obtain electrolyte compositions of Examples C- and C-2 in which the ionic liquid formed a gel.
  • a transparent electrode substrate As a transparent electrode substrate, a 100 mm x 100 mm glass substrate having an FTO film formed thereon was provided, and a slurry dispersion solution of titanium oxide having an average particle diameter of 20 nm was applied on the FTO film (conductive layer) side surface of this transparent electrode substrate 2. After being dried, an oxide semiconductor porous film having a thickness of 7 ⁇ m was obtained by performing heating treatment at 450°C for one hour. The transparent electrode substrate was then immersed overnight in an ethanol solution of ruthenium bipyridine complex (an N3 dye) so as to be sensitized with the dye to form a working electrode. Furthermore, as a counter electrode, an FTO glass electrode substrate was prepared having an electrode layer made of platinum formed thereon by sputtering.
  • the electrolyte composition that was made to gel was applied to the oxide semiconductor porous film of the working electrode, and then the counter electrode and the electrolyte layer were adhered together by overlaying them while pressing the counter electrode hard.
  • a dye-sensitized photovoltaic cell which was a test cell of Example C-1 was fabricated.
  • Electrodes similar to those used in the above-described test cell of Example C-1 were used.
  • an electrolyte solution to form an electrolyte an ionic liquid [1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide] containing iodine/iodide ions as an oxidation-reduction pair was prepared and used.
  • This electrolyte solution was similar to those used to prepare the electrolyte solutions for the electrolyte composition of the test cell of Example C-1, except that insulating particles (C) were not added.
  • a dye-sensitized photovoltaic cell which was the test cell of Comparative Example C-1 was fabricated by placing the working electrode and the counter electrode so that they opposed each other and forming an electrolyte layer by injecting the electrolyte solution therebetween.
  • Japanese Unexamined Patent Application, First Publication No. 2002-184478 discloses a conversion efficiency of a photoelectric conversion element at an early stage of 2.0% when an electrolyte was made into a gel.
  • conversion efficiencies when a gel electrolyte is used have been significantly lower than those when an electrolyte solution is used, which did not occur in the present invention. Accordingly, advantageous effects of making an electrolyte solution (an ionic liquid or the like) into a gel using insulating particles (C) are apparent.
  • the cases where the ionic liquid solutions were a gel (pseudo-solid) by means of addition of these particles (Example C-1) and the cases where the ionic liquid solutions were liquid without addition of the particles (Comparative Examples C-1 and C-2) were compared.
  • a better electrolyte composition could be prepared when the insulating particles (C) were added to the ionic liquid solution (electrolyte solution), compared to cases when they were not added.
  • EMIm-TFSI 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
  • electrolyte compositions of the present invention obtained by blending the above-described liquid electrolyte and insulating particles (C) listed in Table 10 were used.
  • Gel electrolytes of Comparative Examples C-2 and C-3 were obtained by making the liquid electrolyte into a gel (quasi-solid) using the gelling agents listed in Table 11.
  • PVdF-HFP represents a fluororesin-based gelling agent (polyvinylidene fluoride-hexafluoropropylene copolymer).
  • a low molecular weight gelling agent a commercially available low molecular weight gelling agent was used.
  • the gel electrolyte is one having a composition where in insulating particles (C) or gelling agents were added to a liquid electrolyte.
  • a "liquid electrolyte corresponding to a gel electrolyte” refers to a liquid electrolyte having a composition in which the insulating particles (C) or gelling agents are omitted from that gel electrolyte.
  • a diffusion coefficient measured using a liquid electrolyte is termed as a diffusion coefficient in a liquid system
  • a diffusion coefficient measured using a gel electrolyte is termed as a diffusion coefficient in a gel system
  • a rate of change in the diffusion coefficients is termed as (the diffusion coefficient in the gel system - the diffusion coefficient in the liquid system / the diffusion coefficient in the liquid system).
  • An equilibrium potential measured using a liquid electrolyte is termed as an equilibrium potential in a liquid system
  • an equilibrium potential measured using a gel electrolyte is termed as a equilibrium potential in a gel system
  • a shift width of the equilibrium potentials is termed as (the equilibrium potential in the gel system - the equilibrium potential in the liquid system).
  • the measurement conditions for the photoelectric conversion characteristics were photoirradiation conditions with an air mass (AM) of 1.5 and an irradiance of 100 mW/cm 2 .
  • an electrolyte having better characteristics than an ionic liquid (A) itself can be obtained by adding insulating particle (C) into an ionic liquid (A).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Power Engineering (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Mathematical Physics (AREA)
  • Theoretical Computer Science (AREA)
  • Electromagnetism (AREA)
  • Computer Hardware Design (AREA)
  • Hybrid Cells (AREA)
  • Photovoltaic Devices (AREA)
  • Conductive Materials (AREA)

Claims (5)

  1. Elément de conversion photoélectrique comprenant une composition électrolytique qui comprend un liquide ionique et des particules isolantes, dans lequel les particules isolantes sont au moins un élément choisi dans le groupe constitué de diamant et de nitrure de bore,
    le liquide ionique inclut un composé contenant un atome d'azote quatemisé en tant que cation, et
    la composition électrolytique se présente sous la forme d'un gel sous l'action du cation et des particules isolantes.
  2. Elément de conversion photoélectrique selon la revendication 1, dans lequel une quantité incorporée des particules isolantes n'est pas inférieure à 0,05 % en poids et n'est pas supérieure à 70 % en poids par rapport à une quantité totale de la composition électrolytique.
  3. Elément de conversion photoélectrique selon la revendication 1, dans lequel le liquide ionique inclut en outre une paire oxydation-réduction et
    un potentiel d'équilibre de la paire oxydation-réduction dans la composition électrolytique est déplacé vers un potentiel positif dépassant un potentiel d'équilibre de la paire oxydation-réduction dans le liquide ionique.
  4. Elément de conversion photoélectrique selon la revendication 1, comprenant :
    une électrode de travail, l'électrode de travail comprenant un substrat d'électrode et un film poreux semi-conducteur d'oxyde formé sur le substrat d'électrode et sensibilisé à l'aide d'un colorant ;
    une contre-électrode disposée de manière opposée à l'électrode de travail ; et
    une couche d'électrolyte constituée de la composition électrolytique définie à la revendication 1 réalisée entre l'électrode de travail et la contre-électrode.
  5. Cellule photovoltaïque sensibilisée par un colorant, comprenant l'élément de conversion photoélectrique selon la revendication 4.
EP10168992.5A 2003-07-14 2004-07-12 Élément de conversion photoélectrique comportant des particules de diamant ou de nitrure de bore Expired - Lifetime EP2234132B1 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
JP2003196561 2003-07-14
JP2003200629 2003-07-23
JP2003200626 2003-07-23
JP2003347193 2003-10-06
JP2004082934 2004-03-22
JP2004082586 2004-03-22
EP04747709.6A EP1653549B1 (fr) 2003-07-14 2004-07-12 Élément de conversion photoélectrique et cellule solaire à colorant

Related Parent Applications (3)

Application Number Title Priority Date Filing Date
EP04747709.6A Division-Into EP1653549B1 (fr) 2003-07-14 2004-07-12 Élément de conversion photoélectrique et cellule solaire à colorant
EP04747709.6A Division EP1653549B1 (fr) 2003-07-14 2004-07-12 Élément de conversion photoélectrique et cellule solaire à colorant
EP04747709.6 Division 2004-07-12

Publications (3)

Publication Number Publication Date
EP2234132A2 EP2234132A2 (fr) 2010-09-29
EP2234132A3 EP2234132A3 (fr) 2011-03-02
EP2234132B1 true EP2234132B1 (fr) 2014-11-26

Family

ID=34069457

Family Applications (3)

Application Number Title Priority Date Filing Date
EP10168993.3A Expired - Lifetime EP2234133B1 (fr) 2003-07-14 2004-07-12 Élément de conversion photoélectrique comportant des particules d'oxydes semi-conducteurs
EP10168992.5A Expired - Lifetime EP2234132B1 (fr) 2003-07-14 2004-07-12 Élément de conversion photoélectrique comportant des particules de diamant ou de nitrure de bore
EP04747709.6A Expired - Lifetime EP1653549B1 (fr) 2003-07-14 2004-07-12 Élément de conversion photoélectrique et cellule solaire à colorant

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP10168993.3A Expired - Lifetime EP2234133B1 (fr) 2003-07-14 2004-07-12 Élément de conversion photoélectrique comportant des particules d'oxydes semi-conducteurs

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP04747709.6A Expired - Lifetime EP1653549B1 (fr) 2003-07-14 2004-07-12 Élément de conversion photoélectrique et cellule solaire à colorant

Country Status (7)

Country Link
US (3) US8785765B2 (fr)
EP (3) EP2234133B1 (fr)
JP (1) JP4579160B2 (fr)
KR (1) KR100838805B1 (fr)
AU (2) AU2004256669C1 (fr)
TW (1) TWI292225B (fr)
WO (1) WO2005006482A1 (fr)

Families Citing this family (108)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005093307A (ja) * 2003-09-19 2005-04-07 Konica Minolta Medical & Graphic Inc 光電変換素子
JP4997503B2 (ja) * 2004-11-19 2012-08-08 国立大学法人 奈良先端科学技術大学院大学 半導体超微粒子を含有する組成物及びその製造方法
JP2006236807A (ja) * 2005-02-25 2006-09-07 Ngk Spark Plug Co Ltd 色素増感型太陽電池
JP4758684B2 (ja) * 2005-06-14 2011-08-31 セイコーエプソン株式会社 光電変換素子および電子機器
GB0518611D0 (en) * 2005-09-13 2005-10-19 Eastman Kodak Co Transparent conductive system
WO2007063959A1 (fr) 2005-12-02 2007-06-07 Kanto Denka Kogyo Co., Ltd. Liquide ionique contenant un cation phosphonium ayant une liaison p-n et son procede de production
JP5007784B2 (ja) * 2006-01-30 2012-08-22 ソニー株式会社 光電変換装置
KR101202345B1 (ko) 2006-02-06 2012-11-16 삼성디스플레이 주식회사 고전도성 습식 코팅 조성물 및 이로부터 제조된 고전도성박막
JP4857799B2 (ja) 2006-02-10 2012-01-18 セイコーエプソン株式会社 光電変換素子、光電変換素子の製造方法および電子機器
JP5088727B2 (ja) * 2006-03-17 2012-12-05 日本合成化学工業株式会社 リチウム二次電池
US8017860B2 (en) 2006-05-15 2011-09-13 Stion Corporation Method and structure for thin film photovoltaic materials using bulk semiconductor materials
US9105776B2 (en) * 2006-05-15 2015-08-11 Stion Corporation Method and structure for thin film photovoltaic materials using semiconductor materials
JP4062346B2 (ja) * 2006-08-17 2008-03-19 富士ゼロックス株式会社 カーボンナノチューブ膜およびその製造方法、並びにそれを用いたキャパシタ
KR100837808B1 (ko) * 2006-09-13 2008-06-13 한국광기술원 아발란치 광검출기의 제조방법
KR100825730B1 (ko) * 2006-09-28 2008-04-29 한국전자통신연구원 전도성 입자가 분산된 고분자 전해질을 포함하는 염료감응태양전지 및 그 제조 방법
KR100869802B1 (ko) * 2006-11-17 2008-11-21 삼성에스디아이 주식회사 염료감응 태양전지용 전해질, 이를 포함하는 염료감응태양전지, 및 이의 제조방법
KR100924711B1 (ko) * 2006-11-22 2009-11-04 전북대학교산학협력단 타이타니아 나노튜브를 이용한 고분자 전해질 및 이를 이용한 염료감응형 태양전지
US8038853B2 (en) 2007-06-18 2011-10-18 E.I. Du Pont De Nemours And Company Photo-induced reduction-oxidation chemistry of carbon nanotubes
US8071179B2 (en) 2007-06-29 2011-12-06 Stion Corporation Methods for infusing one or more materials into nano-voids if nanoporous or nanostructured materials
JP2009048946A (ja) * 2007-08-22 2009-03-05 Teijin Dupont Films Japan Ltd 色素増感型光電変換素子
US8287942B1 (en) 2007-09-28 2012-10-16 Stion Corporation Method for manufacture of semiconductor bearing thin film material
US8759671B2 (en) 2007-09-28 2014-06-24 Stion Corporation Thin film metal oxide bearing semiconductor material for single junction solar cell devices
US7998762B1 (en) 2007-11-14 2011-08-16 Stion Corporation Method and system for large scale manufacture of thin film photovoltaic devices using multi-chamber configuration
KR100949762B1 (ko) * 2007-12-10 2010-03-25 한국과학기술연구원 복합 전해질 및 그 제조 방법과, 이를 이용한 중공형금속산화물 입자를 포함하는 전해질 기반의 염료감응태양전지
GB2457664A (en) * 2008-02-19 2009-08-26 Science Technology Res Partner Electrolyte composition for a dye sensitized solar cell
JP2009238571A (ja) * 2008-03-27 2009-10-15 Dainippon Printing Co Ltd 色素増感型太陽電池用電解質
US8642138B2 (en) 2008-06-11 2014-02-04 Stion Corporation Processing method for cleaning sulfur entities of contact regions
JP2010009831A (ja) * 2008-06-25 2010-01-14 Tdk Corp 光電変換素子
US9087943B2 (en) 2008-06-25 2015-07-21 Stion Corporation High efficiency photovoltaic cell and manufacturing method free of metal disulfide barrier material
US8003432B2 (en) 2008-06-25 2011-08-23 Stion Corporation Consumable adhesive layer for thin film photovoltaic material
JP5320853B2 (ja) * 2008-06-25 2013-10-23 Ｔｄｋ株式会社 光電変換素子
JP5100573B2 (ja) * 2008-08-27 2012-12-19 株式会社オメガ 電極構造
US7855089B2 (en) 2008-09-10 2010-12-21 Stion Corporation Application specific solar cell and method for manufacture using thin film photovoltaic materials
US8236597B1 (en) 2008-09-29 2012-08-07 Stion Corporation Bulk metal species treatment of thin film photovoltaic cell and manufacturing method
US8008112B1 (en) 2008-09-29 2011-08-30 Stion Corporation Bulk chloride species treatment of thin film photovoltaic cell and manufacturing method
US8008110B1 (en) 2008-09-29 2011-08-30 Stion Corporation Bulk sodium species treatment of thin film photovoltaic cell and manufacturing method
US8394662B1 (en) 2008-09-29 2013-03-12 Stion Corporation Chloride species surface treatment of thin film photovoltaic cell and manufacturing method
US8501521B1 (en) 2008-09-29 2013-08-06 Stion Corporation Copper species surface treatment of thin film photovoltaic cell and manufacturing method
US8026122B1 (en) 2008-09-29 2011-09-27 Stion Corporation Metal species surface treatment of thin film photovoltaic cell and manufacturing method
US8476104B1 (en) 2008-09-29 2013-07-02 Stion Corporation Sodium species surface treatment of thin film photovoltaic cell and manufacturing method
US8425739B1 (en) 2008-09-30 2013-04-23 Stion Corporation In chamber sodium doping process and system for large scale cigs based thin film photovoltaic materials
US8383450B2 (en) 2008-09-30 2013-02-26 Stion Corporation Large scale chemical bath system and method for cadmium sulfide processing of thin film photovoltaic materials
US7947524B2 (en) 2008-09-30 2011-05-24 Stion Corporation Humidity control and method for thin film photovoltaic materials
US7910399B1 (en) 2008-09-30 2011-03-22 Stion Corporation Thermal management and method for large scale processing of CIS and/or CIGS based thin films overlying glass substrates
US7863074B2 (en) 2008-09-30 2011-01-04 Stion Corporation Patterning electrode materials free from berm structures for thin film photovoltaic cells
US8741689B2 (en) 2008-10-01 2014-06-03 Stion Corporation Thermal pre-treatment process for soda lime glass substrate for thin film photovoltaic materials
US20110018103A1 (en) 2008-10-02 2011-01-27 Stion Corporation System and method for transferring substrates in large scale processing of cigs and/or cis devices
US8003430B1 (en) 2008-10-06 2011-08-23 Stion Corporation Sulfide species treatment of thin film photovoltaic cell and manufacturing method
US8435826B1 (en) 2008-10-06 2013-05-07 Stion Corporation Bulk sulfide species treatment of thin film photovoltaic cell and manufacturing method
US8168463B2 (en) 2008-10-17 2012-05-01 Stion Corporation Zinc oxide film method and structure for CIGS cell
DE102008053027A1 (de) * 2008-10-24 2010-04-29 Kme Germany Ag & Co. Kg Verfahren zum Herstellen einer Kohlenstoff-Nanoröhren,Fullerene und/oder Graphene enthaltenden Beschichtung
JP5577586B2 (ja) * 2008-11-20 2014-08-27 大日本印刷株式会社 電解質形成用塗工液、及びそれを用いた色素増感型太陽電池
US8344243B2 (en) 2008-11-20 2013-01-01 Stion Corporation Method and structure for thin film photovoltaic cell using similar material junction
US8338692B2 (en) 2008-11-27 2012-12-25 The Yokohama Rubber Co., Ltd. Electrolyte for photoelectric conversion elements, and photoelectric conversion element and dye-sensitized solar cell using the electrolyte
WO2010061663A1 (fr) * 2008-11-27 2010-06-03 横浜ゴム株式会社 Électrolyte pour élément de conversion photoélectrique, élément de conversion photoélectrique utilisant l'électrolyte, et cellule solaire sensibilisée par un colorant
DE112009003578B4 (de) 2008-11-27 2014-11-27 The Yokohama Rubber Co., Ltd. Elektrolyt für photoelektrische Umwandlungselemente sowie photoelektrisches Umwandlungselement und farbstoffsensibilisierte Solarzelle, die den Elektrolyt verwendet
TW201024267A (en) * 2008-12-19 2010-07-01 Ind Tech Res Inst Electrolyte composition and dye-sensitized solar cell using the same
WO2010074237A1 (fr) * 2008-12-26 2010-07-01 横浜ゴム株式会社 Électrolyte pour élément de conversion photoélectrique et élément de conversion photoélectrique et cellule solaire sensibilisée aux colorants utilisant chacun l'électrolyte
WO2010081170A1 (fr) * 2009-01-12 2010-07-15 Rutgers, The State University Batterie à base de poly(fluorure d'hydrogène)
KR101016099B1 (ko) * 2009-03-02 2011-02-17 주식회사 어플라이드카본나노 염료감응 태양전지용 액상 탄소나노선재를 이용한 태양전지의 상대전극, 이를 포함하는 태양전지와 그 제조방법
JP2010238395A (ja) 2009-03-30 2010-10-21 Tdk Corp 光電変換素子及びその製造方法
JP2010277854A (ja) * 2009-05-28 2010-12-09 Tdk Corp 色素増感型太陽電池、及び、色素増感型太陽電池用の有機溶媒非含有電解質
JP5428555B2 (ja) * 2009-06-08 2014-02-26 ソニー株式会社 色素増感光電変換素子の製造方法
US20100311615A1 (en) 2009-06-09 2010-12-09 Ut-Battelle, Llc Method for synthesis of titanium dioxide nanotubes using ionic liquids
US8507786B1 (en) 2009-06-27 2013-08-13 Stion Corporation Manufacturing method for patterning CIGS/CIS solar cells
JP5521419B2 (ja) * 2009-07-15 2014-06-11 大日本印刷株式会社 電解質形成用塗工液、及びそれを用いた色素増感型太陽電池
US8398772B1 (en) 2009-08-18 2013-03-19 Stion Corporation Method and structure for processing thin film PV cells with improved temperature uniformity
JP2011044357A (ja) * 2009-08-21 2011-03-03 Sony Corp 光電池モジュール及び光電池モジュールの製造方法
US8809096B1 (en) 2009-10-22 2014-08-19 Stion Corporation Bell jar extraction tool method and apparatus for thin film photovoltaic materials
DE102010045073B4 (de) * 2009-10-30 2021-04-22 Taiwan Semiconductor Mfg. Co., Ltd. Elektrische Sicherungsstruktur
JP2011124122A (ja) * 2009-12-11 2011-06-23 Konica Minolta Holdings Inc 電気化学デバイス
US20110162701A1 (en) * 2010-01-03 2011-07-07 Claudio Truzzi Photovoltaic Cells
US20110192462A1 (en) * 2010-01-03 2011-08-11 Alchimer, S.A. Solar cells
US8859880B2 (en) 2010-01-22 2014-10-14 Stion Corporation Method and structure for tiling industrial thin-film solar devices
US8263494B2 (en) 2010-01-25 2012-09-11 Stion Corporation Method for improved patterning accuracy for thin film photovoltaic panels
US20110203644A1 (en) * 2010-02-22 2011-08-25 Brite Hellas Ae Quasi-solid-state photoelectrochemical solar cell formed using inkjet printing and nanocomposite organic-inorganic material
US20110203632A1 (en) * 2010-02-22 2011-08-25 Rahul Sen Photovoltaic devices using semiconducting nanotube layers
US9096930B2 (en) 2010-03-29 2015-08-04 Stion Corporation Apparatus for manufacturing thin film photovoltaic devices
JP4858652B2 (ja) 2010-03-30 2012-01-18 大日本印刷株式会社 色素増感型太陽電池
JP2012004010A (ja) * 2010-06-18 2012-01-05 Sony Corp 光電変換素子およびその製造方法ならびに電子機器
US8461061B2 (en) 2010-07-23 2013-06-11 Stion Corporation Quartz boat method and apparatus for thin film thermal treatment
US8921589B2 (en) 2010-09-30 2014-12-30 Merck Patent Gmbh Electrolyte formulations
US8628997B2 (en) 2010-10-01 2014-01-14 Stion Corporation Method and device for cadmium-free solar cells
US8668984B2 (en) 2010-10-14 2014-03-11 Wnc Solar, Llc Multilayer composite
KR101239966B1 (ko) * 2010-11-04 2013-03-06 삼성전자주식회사 리튬 공기 전지용 양극, 그 제조방법 및 이를 채용한 리튬 공기 전지
US20130139887A1 (en) * 2011-01-07 2013-06-06 Brite Hellas Ae Scalable production of dye-sensitized solar cells using inkjet printing
US8728200B1 (en) 2011-01-14 2014-05-20 Stion Corporation Method and system for recycling processing gas for selenization of thin film photovoltaic materials
US8998606B2 (en) 2011-01-14 2015-04-07 Stion Corporation Apparatus and method utilizing forced convection for uniform thermal treatment of thin film devices
EP2681156A2 (fr) 2011-03-03 2014-01-08 Wisys Technology Foundation Solutions thermodynamiques d'oxydes métalliques et de chalcogénures métalliques, et oxydes et chalcogénures métalliques mélangés
JP2012199096A (ja) * 2011-03-22 2012-10-18 Sony Corp 光電変換素子の製造方法および電子装置の製造方法
JP5662861B2 (ja) * 2011-03-30 2015-02-04 富士フイルム株式会社 光電変換素子及び光電気化学電池
EP2506276A1 (fr) * 2011-03-31 2012-10-03 Bayer MaterialScience AG Cellule solaire sensibilisée par colorant constituée de nanotubes de carbone dotés d'azote
JP2012238444A (ja) * 2011-05-11 2012-12-06 Seiko Epson Corp 高分子固体電解質及びその製造方法、リチウムイオン二次電池
KR101313634B1 (ko) * 2011-06-01 2013-10-02 광주과학기술원 산화아연 반구체를 포함하는 광전극, 그 제조방법 및 이를 이용한 염료감응 태양전지
US8436445B2 (en) 2011-08-15 2013-05-07 Stion Corporation Method of manufacture of sodium doped CIGS/CIGSS absorber layers for high efficiency photovoltaic devices
KR101275636B1 (ko) * 2011-08-30 2013-06-17 전자부품연구원 도핑 폴리머층을 포함하는 그래핀 기반 적층체
TWI467784B (zh) * 2011-12-21 2015-01-01 Univ Nat Cheng Kung 太陽能電池
JP5889006B2 (ja) * 2012-01-31 2016-03-22 大阪瓦斯株式会社 電解質ゲル及び光電変換素子
JP5274691B1 (ja) * 2012-05-30 2013-08-28 株式会社フジクラ 色素増感太陽電池
US20140298762A1 (en) * 2013-04-03 2014-10-09 William A Kelley Nano Filter Pump
US10315164B2 (en) 2013-04-03 2019-06-11 William A. Kelley Nanoscale gaseous material filtering and pumping systems and methods of use thereof
TWI571898B (zh) * 2014-05-15 2017-02-21 國立虎尾科技大學 A flexible supercapacitor method with porous electrodes
US9711293B1 (en) * 2015-01-07 2017-07-18 The United States Of America, As Represented By The Secretary Of The Navy Capacitor with ionic-solution-infused, porous, electrically non-conductive material
JP6576784B2 (ja) * 2014-12-26 2019-09-18 株式会社フジクラ 光電変換素子用電解質、及び、これを用いた光電変換素子
JP7090400B2 (ja) * 2017-03-08 2022-06-24 浜松ホトニクス株式会社 半導体光検出素子
JP7304567B2 (ja) * 2019-02-14 2023-07-07 株式会社ダイセル ナノダイヤモンド分散組成物
JP7543642B2 (ja) * 2019-11-25 2024-09-03 株式会社リコー 液体組成物、液体吐出方法、電極の製造方法及び電気化学素子の製造方法
CN112619701B (zh) * 2021-01-19 2021-12-07 河海大学 一种制备染料-氮化硼复合光催化材料的方法及应用

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4189827A (en) * 1978-11-03 1980-02-26 The United States Of America As Represented By The United States Department Of Energy Treatment of electrochemical cell components with lithium tetrachloroaluminate (LiAlCl4) to promote electrolyte wetting
CH674596A5 (fr) 1988-02-12 1990-06-15 Sulzer Ag
US5128006A (en) * 1991-01-23 1992-07-07 At&T Bell Laboratories Deposition of diamond films on semicondutor substrates
WO1995018456A1 (fr) 1993-12-29 1995-07-06 Ecole Polytechnique Federale De Lausanne Pile photo-electrochimique et electrolyte pour cette pile
JP3103507B2 (ja) 1996-06-07 2000-10-30 株式会社石塚研究所 不純ダイヤモンド粉末の精製法
EP0855726B1 (fr) * 1997-01-22 2006-01-25 Greatcell Solar S.A. Cellule solaire et procédé de fabrication
US6683783B1 (en) * 1997-03-07 2004-01-27 William Marsh Rice University Carbon fibers formed from single-wall carbon nanotubes
JP3472133B2 (ja) * 1998-04-17 2003-12-02 Ｔｄｋ株式会社 リチウム二次電池、および電気二重層キャパシタの製造方法
JP3587982B2 (ja) 1998-04-17 2004-11-10 Ｔｄｋ株式会社 高分子固体電解質およびこれを用いたリチウム二次電池と電気二重層キャパシタ
JP3946947B2 (ja) 1999-09-24 2007-07-18 株式会社東芝 光増感型太陽電池用電解質組成物、光増感型太陽電池及び光増感型太陽電池の製造方法
JP2001229967A (ja) * 2000-02-10 2001-08-24 Mitsui Chemicals Inc ゲル状電解質およびリチウム電池
US6878492B2 (en) 2000-07-10 2005-04-12 Showa Denko Kabushiki Kaisha Polymerizable composition and use thereof
JP4799776B2 (ja) 2000-08-22 2011-10-26 富士フイルム株式会社 電解質組成物及びそれを用いた電気化学電池
US6301039B1 (en) 2000-09-13 2001-10-09 Rockwell Technologies, Llc Reversible electrochemical mirror (REM) state monitoring
JP2002184478A (ja) 2000-12-15 2002-06-28 Fuji Xerox Co Ltd 電解質、光電変換素子、光電気化学電池および電解質の製造方法
JP5081352B2 (ja) 2001-08-22 2012-11-28 トーメイダイヤ株式会社 炭化物被覆ダイヤモンド粉末の製造方法
US7232790B2 (en) * 2001-09-11 2007-06-19 Showa Denko K.K. Activated carbon, method for production thereof and use thereof
JP2003157719A (ja) * 2001-11-22 2003-05-30 Hitachi Maxell Ltd 常温溶融塩型固体電解質およびそれを用いた全固体電気化学素子
JP2003157914A (ja) * 2001-11-22 2003-05-30 Fuji Photo Film Co Ltd 光電変換素子、光電変換素子の製造方法、及び光電池
WO2003054894A1 (fr) * 2001-12-21 2003-07-03 Sony International (Europe) Gmbh Pile solaire hybride a gel polymere
AU2003237782A1 (en) * 2002-03-04 2003-10-20 William Marsh Rice University Method for separating single-wall carbon nanotubes and compositions thereof
JP4392741B2 (ja) 2002-04-17 2010-01-06 日揮触媒化成株式会社 光電気セル
AU2003268729A1 (en) 2002-10-03 2004-05-04 Daikin Industries, Ltd. Fluorine-containing polymer solid electrolyte having fluorine-containing ether chain
EP1473745A1 (fr) 2003-04-30 2004-11-03 Ecole Polytechnique Federale De Lausanne (Epfl) Cellule solaire sensibilisée par colorant

Also Published As

Publication number Publication date
TWI292225B (en) 2008-01-01
EP2234132A2 (fr) 2010-09-29
EP2234133B1 (fr) 2014-12-03
AU2004256669A1 (en) 2005-01-20
US20090253031A1 (en) 2009-10-08
EP2234133A2 (fr) 2010-09-29
EP2234132A3 (fr) 2011-03-02
US7872191B2 (en) 2011-01-18
WO2005006482A1 (fr) 2005-01-20
AU2010235977A1 (en) 2010-11-11
EP1653549A4 (fr) 2009-08-12
EP1653549B1 (fr) 2016-02-17
AU2010235977B2 (en) 2011-09-08
US8785765B2 (en) 2014-07-22
EP1653549A1 (fr) 2006-05-03
US20090293953A1 (en) 2009-12-03
TW200507287A (en) 2005-02-16
KR20060038992A (ko) 2006-05-04
AU2004256669B2 (en) 2007-05-24
US20060174932A1 (en) 2006-08-10
US8790551B2 (en) 2014-07-29
AU2004256669C1 (en) 2009-09-24
KR100838805B1 (ko) 2008-06-17
EP2234133A3 (fr) 2011-03-09
JP4579160B2 (ja) 2010-11-10
JPWO2005006482A1 (ja) 2006-08-24

Similar Documents

Publication Publication Date Title
EP2234132B1 (fr) Élément de conversion photoélectrique comportant des particules de diamant ou de nitrure de bore
AU2007252623B2 (en) Method of manufacturing electrode substrate, electrode substrate, photoelectric conversion element, and dye-sensitized solar cell
US7422922B2 (en) Photoelectric conversion element and process for fabricating the same, electronic device and process for fabricating the same
KR100825730B1 (ko) 전도성 입자가 분산된 고분자 전해질을 포함하는 염료감응태양전지 및 그 제조 방법
KR100869816B1 (ko) 전해질 조성물 및 이것을 사용한 광전변환 소자
JP5075913B2 (ja) 電解質組成物およびこれを用いた光電変換素子
EP1675211B1 (fr) Composition d'electrolyte et convertisseur photoelectrique utilisant cette composition
JP4522673B2 (ja) 電解質組成物、これを用いた光電変換素子および色素増感太陽電池
JP4420645B2 (ja) 低温型有機溶融塩、光電変換素子及び光電池
Farhana et al. Sonochemically tailored Copper Oxide as nanofiller in terpolymer composite gel electrolytes for dye-sensitized solar cells
KR101006078B1 (ko) 고체형 나노복합 전해질 및 이를 이용한 태양전지
AU2007202985B2 (en) Electrolyte composition, and photoelectric converter and dye-sensitized solar cell using same
JP4772311B2 (ja) 電解質組成物、これを用いた光電変換素子及び色素増感太陽電池、並びにイオン性液体の評価方法
Mozaffari et al. Nateghi & Mahmood Borhanizarandi
WO2010061663A1 (fr) Électrolyte pour élément de conversion photoélectrique, élément de conversion photoélectrique utilisant l'électrolyte, et cellule solaire sensibilisée par un colorant

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20100709

AC Divisional application: reference to earlier application

Ref document number: 1653549

Country of ref document: EP

Kind code of ref document: P

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT CH DE FI LI NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT CH DE FI LI NL SE

17Q First examination report despatched

Effective date: 20111222

RIC1 Information provided on ipc code assigned before grant

Ipc: H01L 51/44 20060101AFI20140702BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20140808

RIC1 Information provided on ipc code assigned before grant

Ipc: H01G 9/20 20060101AFI20140729BHEP

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AC Divisional application: reference to earlier application

Ref document number: 1653549

Country of ref document: EP

Kind code of ref document: P

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT CH DE FI LI NL SE

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 698602

Country of ref document: AT

Kind code of ref document: T

Effective date: 20141215

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602004046232

Country of ref document: DE

Effective date: 20150108

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20141126

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 698602

Country of ref document: AT

Kind code of ref document: T

Effective date: 20141126

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141126

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141126

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141126

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141126

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602004046232

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20150827

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150731

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150731

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20160705

Year of fee payment: 13

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602004046232

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180201